High surface hardness transparent resin prepared from a compound having at least one isopropenyl phenyl group

ABSTRACT

The present invention relates to a high surface hardness transparent resin having excellent scratch resistance, heat resistance and chemical resistance, a glazing material, a protective cover for display devices, an optical lens and a hard coat material comprising the aforesaid resin, and a novel polymerizable monomer which is useful as a raw material of the above-mentioned resin. 
     The monomer is represented by the formula (I) ##STR1## (wherein R is an aliphatic residue having or not having an halogen atom, an oxygen atom, an alicyclic ring, a heterocyclic ring or an aromatic ring, an alicyclic residue, or a heterocyclic residue, n is an integer of 1 to 4, when n=1, X is oxygen or sulfur, when n≧2, X&#39;s are all oxygen or all sulfur, one X is oxygen while the other X or X&#39;s are sulfur, one X is sulfur while the other X or X&#39;s are oxygen, or two X&#39;s are oxygen while the other X&#39;s are sulfur). 
     The aforesaid high surface hardness transparent resin comprises a crosslinked polymer prepared by copolymerizing a monomer (A) represented by the formula (I) and a monomer (B) having, in one molecule, m functional groups of at least one kind selected from the group consisting of CH 2  ═CH--C(O)--O--, CH 2  ═C(CH 3 )--C(O)--O-- and ##STR2## where (n+m) is an integer of 3 or more.

BACKGROUND OF THE INVENTION

(i) Field of the Invention

The present invention relates to a transparent resin which has highsurface hardness and exhibits excellent scratch resistance, heatresistance and chemical resistance. The invention also relates to aglazing material, a protective cover for display devices, an opticallens and a hard coat material comprising the resin and a novelpolymerizable monomer useful as a raw material for the high surfacehardness transparent resin.

(ii) Description of the Prior Art

Methacrylic resin, polycarbonate resin and polystyrene resin exhibitexcellent transparency, impact resistance, workability and massproductivity, and therefore have been used as a glazing material such asfor windowpanes in vehicles, houses, schools and sports facilities,baseboards of verandas, and balconies, protective covers for displaydevices such as various dashboards, displays for computers, liquidcrystal televisions and front boards of vending machines, opticallenses, illuminator covers, signboards, protective glasses, opticalphotodisc substrates and the like. Particularly, when theabove-mentioned resins are applied as glazing materials, protectivecovers for display devices and as optical lenses, it is necessary thatsuch resins have high scratch resistance, i.e., high surface hardness,chemical resistance, heat resistance and the like to achieve goodvisibility and desired appearance transparency, optical physicalproperties, mechanical strength stiffness and the like.

However, the above-mentioned transparent resins are linear polymers, andtherefore do not exhibit the requisite surface hardness, chemicalresistance and heat resistance. In addition, even if these resins arecoated with a hard coat to improve their surface hardness and chemicalresistance, sufficient performance cannot always be obtained.

For the purpose of solving these problems, a transparent resin has beenproposed which comprises a polymer having a crosslinking structure suchas diethylene glycol diallylcarbonate resin or a urethane polyacrylate(Japanese Patent Laid-open Publication Nos. 3610/1986 and 75022/1988).

However, the proposed resins are prepared by the mutual polymerizationof an allyl group, an acrylic group or a methacylic group,polymerization rates of which are on a similar and therefore problemsexist such as difficulty of controlling the rate of polymerizationrun-away reactions and a long period of time is required to obtain apolymer having a good surface state and a low polymerization strain.

SUMMARY OF THE INVENTION

invention overcomes the problems and disadvantages of the prior art byproviding a high surface hardness transparent resin prepared bycombining an isopropenylphenyl group having a low polymerization ratewith another polymerizable group having a high polymerization rate, i.e.by copolymerizing a compound having at least one isopropenylphenylgroups in one molecule thereof and another compound having an acryloylgroup, a methacryloyl group or a vinylphenyl group in which the radicalpolymerizability is higher than in the isopropenylphenyl group.

An object of the present invention is to provide a transparent resinwhich can be prepared by an easily controlled polymerization reactionand which has a high surface hardness and exhibits excellent chemicalresistance and heat resistance.

Another object of the present invention is to provide a monomer having apolymerizable group which has a polymerization rate slower than anacrylic group, a methacrylic group and a vinylphenyl group and whichexhibits excellent copolymerizability with these groups, and which canbe formed into a polymer having a high surface hardness and excellenttransparency, heat resistance and chemical resistance properties.

Additional objects and advantages of the invention will be set forth inpart in the description which follows, and in part will be obvious fromthe description, or may be learned by practice of the invention. Theobjects and advantages of the invention will be realized and attained bymeans of the instrumentalities and combination, particularly pointed outin the appended claims.

To achieve the objects and in accordance with the purpose of theinvention, as embodied and broadly described herein, in a firstembodiment, the present invention provides a high surface hardnesstransparent resin comprising a crosslinked polymer prepared bycopolymerizing a monomer (A) represented by the formula (I) ##STR3##(wherein R is an aliphatic residue having or not having a halogen atom,an oxygen atom, an alicyclic ring, a heterocyclic ring or an aromaticring, an alicyclic residue, or a heterocyclic residue, n is an integerof 1 to 4, when n=1, X is oxygen or sulfur, when n≧2, X's are all oxygenor all sulfur, one X is oxygen while the other X or X's are sulfur, oneX is sulfur while the other X or X's are oxygen, or two X's are oxygenwhile the other X's are sulfur) and a monomer (B) having, in onemolecular, m functional groups of at least one kind selected from thegroup consisting of CH₂ ═CH--C(O)--O--, CH₂ ═C(CH₃)--C(O)--O-- and##STR4## where (n+m) is an integer of 3 or more.

In a second embodiment, the present invention provides a high surfacehardness transparent resin comprising a crosslinked polymer containing astructural unit represented by the following formula (II) and/or (III)comprising the monomer (A) and the monomer (B) set forth above: ##STR5##(wherein X is oxygen or sulfur, R is an aliphatic residue having or nothaving a halogen atom, an oxygen atom, an alicyclic ring, a heterocyclicring or an aromatic ring, an alicyclic residue, or a heterocyclicresidue, R' is hydrogen or methyl, Y is, similar or dissimilar, ##STR6##n is an integer of 1-4, and ( n+m ) is an integer of 3 or more).

In a third embodiment, the present invention provides a glazing materialcomprising a high surface hardness transparent resin described in thefirst embodiment of the invention.

In a fourth embodiment the present invention provides a protective coverfor display devices comprising the high surface hardness transparentresin described in the first embodiment of the invention.

In a fifth embodiment the present invention provides an optical lenscomprising the high surface hardness transparent resin described in thefirst embodiment of the invention.

In sixth embodiment the present invention provides a hard coat materialcomprising the high surface hardness transparent resin described in thefirst embodiment of the present invention.

In a seventh embodiment of the present invention provides a high surfacehardness transparent resin comprising a crosslinked polymer prepared bycopolymerizing a monomer (A) of at least one kind selected from thegroup consisting of monomers represented by the formulae (IV), (V) and(VI). ##STR7## wherein when n is 1, R is selected from the groupconsisting of --CH₃, --C₂ H₅, --C₃ H₇, --C₄ H₉, --C₅ H₁₁, --C₆ H₁₃,--CH₂ CCl₃, --CH₂ CF₃, ##STR8## and the substituent on the aromatic ringis present at the m-position or the p-position thereof, ##STR9## whereinwhen n is 2, R is selected from the group consisting of--(CH₂)i--(i=2-6), ##STR10## and the substituent on the aromatic ring ispresent at the m-position or the p-position thereof, ##STR11## whereinwhen n is 3, R is selected from the group consisting of ##STR12## andthe substituent on the aromatic ring is present at the m-position or thep-position thereof and a monomer (B) having, in one molecular, mfunctional groups of at least one kind selected from the groupconsisting of CH₂ ═CH--C(O)--O--, CH₂ ═C(CH₃)--C(O)--O-- and ##STR13##where the sum of (n+m) is an integer of 3 or more.

In an eighth embodiment of the present invention is directed to apolymerizable monomer represented by the formula (I), especially, theformula (VII) below, ##STR14## wherein n is 2 or 3, R is selected fromthe group consisting of ##STR15## and the substituent on the aromaticring is present at the m-position or the p-position thereof.

The inventors have found that run-away reactions can be easilycontrolled during polymerization; and polymerization time can benoticeably shortened.

In addition, it has also been found that the resin of the presentinvention has a high surface hardness, i.e., scratch resistance, heatresistance and chemical resistance, and therefore plate materialscomprising this resin are useful as glazing materials such aswindowpanes in vehicles houses, schools and sports facilites, baseboardsof verandas, and balconies, protective covers for display devices suchas various dashboards, displays for computers, liquid crystaltelevisions and front boards of vending machines, and optical lenses.Furthermore, it has been found that the resin of the present inventionis also useful as a coating film, i.e., hard coat material, because whenthe resin is applied onto a resin, a metal or a lumber material and thenpolymerized, the obtained hard coat has excellent scratch resistance andchemical resistance.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Reference will now be made in detail to the present preferredembodiments of the invention.

Exemplary suitable monomers (A) represented by the following formula (I)of the present invention ##STR16## (wherein R is an aliphatic residuehaving or not having a halogen atom, an oxygen atom, an alicyclic ring,a heterocyclic ring or an aromatic ring, an alicyclic residue, or aheterocyclic residue, n is an integer of 1 to 4, when n=1, X is oxygenor sulfur, when n≧2, X's are all oxygen or all sulfur, one X is oxygenwhile the other X or X's are sulfur, one X is sulfur while the other Xor X's are oxygen, or two X's are oxygen while the other X's are sulfur)include a carbamic acid ester or a thiocarbamic acid ester obtained byreacting isopropenyl-α-α-dimethylbenzyl isocyanate with a compoundhaving from 1 to 4 OH groups or SH groups and an aliphatic residue whichmay or may not contain a halogen atom, an oxygen atom, an alicyclicring, a hetrocyclic ring or aromatic ring, an alicyclic residue or aheterocyclic residue, i.e., reacting the isocyanate group ofisopropenyl-α,α-dimethylbenzyl isocyanate with the OH group or SH group.Here, compounds of the formula (I) where when n is 2 or more, X's areall oxygen or all sulfur, or when one or two X's are oxygen and theother X being sulfur, or one X is sulfur and the other X being oxygen,can be included.

Usually, the lower the molecular weight of the residue R, the better,depending upon the steric firmness of its structure. Preferably, themolecular weight of the residue R is from 15 to 500. Exemplary suitablecompounds having from 1 to 4 OH groups or SH groups and an aliphaticresidue which may or may not have a halogen atom, an oxygen atom, analicyclic ring, a heterocyclic ring or an aromatic ring, an alicyclicresidue or a heterocyclic residue which are used in preparing themonomer (A) by the above-mentioned method include methanol, ethanol,propanol, butanol, pentanol, hexanol, heptanol, octanol, cyclopentanol,cyclohexanol, cycloheptanol, cyclooctanol, 2,2,2-trichloroethanol,2,2,2-trifluoroethanol, 1,3-dichloro-2-propanol,2,3-dichloro-1-propanol, 2,3-dibromo-1-propanol, 1-chloro-2-propanol,3-chloro-1-propanol, 2-chloroethanol, 2-bromoethanol, methanethiol,ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol,heptanethiol, octanethiol, cyclohexanethiol, benzyl alcohol, ethyleneglycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol,1,5-pentanediol, 1,6-hexanediol, 1,2-propanediol, 1,3-butanediol,2,3-butanediol, 2,5-hexanediol, diethylene glycol, neopentyl glycol,3-methyl-1,5-pentanediol, dipropylene glycol, triethylene glycol,1,2-butanediol, 2-ethyl-1,3-hexanediol, spiro glycol,1,4-cyclohexanediol, tricyclo[5,2,1,0²,6 ]decane-4,8-dimethanol,3-chloro- 1,2-propanediol, 3-bromo-1,2-propanediol,2,3-dibromo-1,4-butanediol, dibromoneopentyl glycol, bisphenol A(2-hydroxyethyl) ether, bisphenol F (2-hydroxyethyl) ether, bisphenol S(2-hydroxyethyl) ether, biphenol (2-hydroxyethyl) ether,tetrabromobisphenol A (2-hydroxyethyl) ether, benzenedimethanol,ethanedithiol, propanedithiol, butanedithiol, pentanedithiol,hexanedithiol, propanetrithiol, cyclohexanedithiol, ethylene glycolbis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate),bis(mercaptomethyl)benzene, 2-hydroxyethyl disulfide, 2-mercaptoethanol,1-mercapto-2-propanol, glycerol, trimethylolethane, trimelthylolpropane,1,2,4-butanetriol, 1,2,6-hexanetriol, 1,3,5-tris(2-hydroxyethyl)cyanuricacid, pentaerythritol, threitol, 3-mercapto-1,2-propanediol,pentaerythritol tetrakis(2-mercapto acetate) and pentaerythritoltetrakis(3-mercapto propionate). The carbamic acid ester or thiocarbamicacid ester can be produced from the above-mentioned compounds by thereaction between the isocyanate group of isopropenyl-α-α-dimethylbenzylisocyanate and the OH group or the SH group. At this time, a tincompound such as dibutyltin dilaurate, dimethyltin dichloride and thelike or an amine such as morpholine, dimethylaminobenzene and the likemay be added thereto as a catalyst to accelerate the synthetic reaction.Preferably, a tin compound is added to prevent coloring in a subsequentradical reaction. When a solvent is used, the solvent should bedistilled off after completion of the synthetic reaction. If necessary,purification may be further carried out, and the thus obtained productmay be used as the monomer (A) in the subsequent radical polymerization.

Exemplary suitable monomers (A) for use in the invention includecompounds represented by the formulae (IV), (V) and (VI): ##STR17##wherein when n is 1, R is selected from the group consisting of --CH₃,--C₂ H₅, --C₃ H₇, --C₄ H₉, --C₅ H₁₁, --C₆ H₁₃, --CH₂ CCl₃, --CH₂ CF₃,##STR18## and the substituent on the aromatic ring is present at them-position or the p-position thereof. ##STR19## wherein when n is 2, Ris selected from the group consisting of --(CH₂)i--wherein i=2-6,##STR20## wherein i=1 or 2, ##STR21## and the substituent on thearomatic ring is present at the m-position or the p-position thereof.##STR22## wherein when n is 3, R is selected from the group consistingof ##STR23## and the substituent on the aromatic ring is present at them-position or the p-position thereof. Further examples of the monomer(A) are: ##STR24## (wherein n=4, R is ##STR25## the substituents on thearomatic ring are at m- or p-position), ##STR26## (wherein n=2, R is--(CH₂)i--(i=2-6), ##STR27## the substituents on the aromatic ring areat m- or p-position), and ##STR28## (wherein R2 is H or --CH₃, thesubstituents on the aromatic ring are at m- or p-position).

The monomer B having m functional groups of one kind selected from thegroup consisting of ##STR29## in the present invention is an ester ofacrylic acid or methacrylic acid or a derivative of styrene. Exemplarysuitable monomers (B) in which m is 1 for use in the invention includemethyl acrylate, methyl methacrylate, ethyl acrylate, ethylmethacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate,isopropyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,benzyl acrylate, benzyl methacrylate, methoxyethyl acrylate,methoxyethyl methacrylate, ethoxyethyl acrylate, ethoxyethylmethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 1,4-butyleneglycol monoacrylate, 1,4-butylene glycol monomethacrylate, glycidylacrylate, glycidyl methacrylate, styrene, methylstyrene, chlorostyrene,bromostyrene, chloromethylstyrene and methoxystyrene.

Exemplary suitable monomers (B) in which m is 2 or more include ethyleneglycol diacrylate, ethylene glycol dimethacrylate, diethylene glycoldiacrylate, diethylene glycol dimethacrylate, propylene glycoldiacrylate, propylene glycol dimethacrylate, dipropylene glycoldiacrylate, dipropylene glycoldimethacrylate,,2,2-bis(4-acryloxyethoxyphenyl)propane,2,2-bis(4-methacryloxyethoxyphenyl)propane,2,2-bis(4-acryloxydiethoxyphenyl)propane,2,2-bis(4-methacryloxydiethoxyphenyl)propane,2,2-bis(4-acryloxypropyloxyphenyl)propane,2,2-bis(4-methacryloxypropyloxyphenyl)propane, 1,3-butanedioldiacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate,1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanedioldimethacrylate, neopentyl glycol diacrylate, neopentyl glycoldimethacrylate, neopentyl glycol hydroxypivalate diacrylate, spiroglycoldiacrylate, spiroglycol dimethacrylate, epoxy acrylate, epoxymethacrylate, 2-propenoic acid[2-[1,1-dimethyl-2-[(1-oxo-2-propenyl)oxy]ethyl]-5-ethyl-1,3-dioxane-5-yl]methylester, trimethylolpropane triacrylate, trimethylolpropanetrimethacrylate, pentaerythritol triacrylate, pentaerythritoltrimethacrylate, bis(acryloyloxyethyl)hydroxyethyl isocyanurate,bis(methacryloyloxyethyl)hydroxyethyl isocyanurate,tris(acryloyloxyethyl) isocyanurate, tris(methacryloyloxyethyl)isocyanurate, pentaerythritol tetraacrylate, pentaerythritoltetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritolhexamethacrylate, methyltri(acryloyloxyethoxy)silane, glyceroldiacrylate, glycerol dimethacrylate, glycerol methacrylate acrylate,dibromoneopentyl glycol diacrylate, dibromoneopentyl glycoldimethacrylate, divinylbenzene, urethane acrylates, urethanemethacrylates, 1,1,3,3,5,5-hexa(acryloyloxy)cyclotriphosphazene,1,1,3,3,5,5-hexa(methacryloyloxy)cyclotriphosphazene,1,1,3,3,5,5-hexa(acryloylethylenedioxy)cyclotriphasphozene and1,1,3,3,5,5-hexa(methacryloylethylenedioxy)cyclotriphosphazene.

In the present invention, the transparent resin having a high surfacehardness can be prepared by copolymerizing a monomer (A) represented bythe formula (I) ##STR30## (wherein R is an aliphatic residue having ornot having a halogen atom, an oxygen atom, an alicyclic ring, aheterocyclic ring or an aromatic ring, an alicyclic residue, or aheterocyclic residue, n is an integer of 1 to 4, when n=1, X is oxygenor sulfur, when n≧2, X's are all oxygen or all sulfur, one X is oxygenwhile the other X or X's are sulfur, one X is sulfur while the other Xor X's are oxygen, or two X's are oxygen while the other X's are sulfur)and a monomer (B) having, in one molecule, m functional groups of atleast one kind selected from the group consisting of CH₂ ═CH--C(O)--O--,CH₂ ═C(CH₃)--C(O)--O-- and ##STR31## in such a ratio that (n+m) is aninteger of 3 or more.

For the purpose of adjusting viscosity and the like, a monomer having anisopropenylphenyl group other than the above-mentioned monomer (A) maybe additionally used.

Exemplary suitable additional monomers include diisopropenylbenzene,N-(3-isopropenyl-α,α-dimethylbenzyl)-2-acryloyloxy carbamate andN-(3-isopropenyl-α,α-dimethlbenzyl)-2-methacryloyloxy carbamate.

In this copolymerization, the ratio of the isopropenyl group to##STR32## in the above-mentioned monomers depends on the type offunctional groups in the monomers and the structures of the monomers.Preferably the copolymerization is carried out in a ratio of theisopropenylphenyl group: the total of ##STR33## of 1 equitalent: 0.5-10equivalents. The copolymerization in the present invention is a radicalcopolymerization and can be accomplished by heat polymerization or by ameans using ultraviolet rays, γrays, or the like or a combinationthereof.

When the heat polymerization is carried out, the radical polymerizationinitiator is not limited to any particular one, but a known radicalpolymerization initiator can optionally be used. Exemplary suitableinitiators include peroxides such as benzoyl peroxide, p-chlorobenzoylperoxide, diisopropyl peroxy carbonate, di-2-ethylhexyl peroxy carbonateand carbonate and t-butylperoxy pivalate and an azo compound such asazobisisobutyronitrile. This intiator preferably used in an amount offrom 0.01 to 5% by weight.

When the ultraviolet rays are utilized, the optical sensitizer is notparticularly limited, but a known optical sensitizer can optionally beused.

Exemplary suitable sensitizers include benzoyl compounds, benzoin methylether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutylether, 2-hydroxy-2-benzoylpropane, azobisisobutyronitrile, benzil,thioxanthone and diphenyl disulfide. This sensitizer is preferably usedin an amount of from 0.01 to 5% by weight. When a radiation such as γrayand the like is utilized, the polymerization initiator and the like arenot always necessary.

In the present invention, the process for preparing plates or lenses ofthe high surface hardness, transparent resin is not particularlylimited. Known processes can be used. A typical process is a castingpolymerization process. For example, a mixture of the above-mentionedmonomers is mixed with a radical polymerization initiator or an opticalsensitizer sufficiently, followed by defoaming. Afterward, the mixtureis poured into a glass or metallic mold with which a gasket or a spaceris combined, and is then cured by heating or the irradiation byultraviolet rays or radiation. Additives may be added to the mixtureprior to polymerization. Exemplary suitable additives includeultraviolet absorbents, oxidation inhibitors, dyes, infrared absorbents,release agents and antistatic agents.

These additives should be used in amounts such that they do not preventpolymerization and curing.

When the high surface hardness transparent resin is used for thepreparation of coating films, a known coating film manufacturing processmay be employed. For example, a radical polymerization initiator or anoptical sensitizer is added to a mixture of the above-mentionedmonomers, and if necessary, the mixture is diluted with a solvent.Afterward, a substrate made of a resin, a metal, a lumber material orthe like is coated with the mixture by roll coating, spray coating, flowcoating, dipping or the like. When the solvent is used, it isvolatilized, and curing is then carried put by heating or by theirradiation by ultraviolet rays or radiation. In this case, additives, afiller and the like can be added to the mixture prior to thepolymerization. Exemplary suitable additives include an ultravioletabsorbents, oxidation inhibitors, dyes, pigments, infrared absorbents,antistatic agents and fine inorganic compound grains. These additivesshould be used in amount such that they do not prevent thepolymerization and curing.

The thus obtained high surface hardness transparent resin plate can beused as a glazing material and a protective cover for display devicesand has high scratch resistance, chemical resistance, heat resistanceand excellent workability. In addition, when polymerization is carriedout in a mold for lenses, or when the resin is processed by cutting andpolishing, optical lenses having the same characteristics as in theabove case can be obtained.

Morever, the high-hardness transparent resin can be used as a coatingmaterial, i.e., a hard coat material that exhibits excellent scratchresistance, chemical resistance and the like on another resin, a metal,a lumber material or the like.

The novel polymerizable monomer of the present invention is theabove-mentioned monomer (A). Exemplary suitable polymerizable monomersinclude 1,2-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]ethane,1,2-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]ethane,1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]2-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]ethane,1,3-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,1,3,-bis[N-(4-isopropenyl-α, α-dimethylbenzyl)carbamoyloxy]propane,1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]3-[N-4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,1,4-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1,4-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]4-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1,5-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]pentane,1,5-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]pentane,1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-5-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]pentane,1,6-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]hexane,1,6-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]hexane,1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-6-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]hexane,1,2-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,1,2-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-2-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,1,3-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1,3-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-3-(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,2,3-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,2,3-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,2-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-3-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,2,5-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]hexane,2,5-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]hexane,2-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-5-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]hexane,bis[2-(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethyl]ether,bis[2-(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethyl]ether,[2-(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethyl]-[2'-(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethyl]ether,2,2-dimethyl-1,3-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,2,2-dimethyl-1,3-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,2,2-dimethyl-1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-3-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,3-methyl-1,5-bis[N-(3-isopropenyl-α,α- dimethylbenzyl)carbamoyloxy]pentane,3-methyl-1,5-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]pentane,3-methyl-1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-5-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]pentane,bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)isopropyl]ether,bis[(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)isopropyl]ether,[(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)isopropyl][(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)isopropyl]ether,bis[2-(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethoxy]ethane,bis[2-(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethoxy]ethane,[2-(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethoxy]-[2'-(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethoxy]ethane,1,2-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1,2-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-2-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-2-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,2-ethyl-1,3-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]hexane,2-ethyl-1,3-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]hexane,2-ethyl-1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-3-[N-(4-isopropenylα,α-dimethylbenzyl)carbamoyloxy]hexane,2-ethyl-1-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-3-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]hexane,3,9-bis[1,1-dimethyl-2-(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane,3,9-bis[1,1-dimethyl-2-(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane,3-[1,1-dimethyl-2-(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethyl]-9-[1,1-dimethyl-2-(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane,1,4-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]cyclohexane,1,4-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]cyclohexane,1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-4-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]cyclohexane,4,8-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]tricyclo[5,2,1,0²,6]decane,4,8-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]tricyclo[5,2,1,0²,6]decane,4-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]-8-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]tricyclo[5,2,1,0²,6]decane;3-chloro-1,2-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,3-chloro-1,2-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,3-chloro-1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-2-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,3-chloro-1-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-2-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,3-bromo-1,2-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,3-bromo-1,2-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,3-bromo-1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-2-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,3-bromo-1-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-2-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,2,3-dibromo-1,4-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,2,3-dibromo-1,4-bis[N'-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,2,3-dibromo-1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-4-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,2,2-dibromomethyl-1,3-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,2,2-dibromomethyl-1,3-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,2,2-dibromomethyl-1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]3-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,1,2,3-tris[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,1,2-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-3-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,1,3-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-2-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,1,2-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-3-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,1,3-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-2-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,1,2,3-tris[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,1,1,1-tris[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]ethane,1,1-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]-1-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]ethane,1,1-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]-1-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]ethane,1,1,1-tris[N-(4-ispropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]ethane,2-ethyl-2-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]-1,3-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,2-ethyl-2-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]-1,3-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,2-ethyl-2-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]-1,3-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,2-ethyl-2-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]-1,3-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane,1,2,4-tris[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1,2-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-4-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1,4-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-2-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1,2-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-4-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1,4-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-2-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1,2,4-tris[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane,1,3,5-tris[2-(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxyethyl)]isocyanurate,1,3-bis[2-(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxyethyl)]-5-[2-(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxyethyl)]isocyanurate,1,3-bis[2-(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxyethyl)]-5-[2-(N-(3-isopropenyl-α,α-dimethybenzyl)carbamoyloxyethyl)]isocyanurateand1,3,5-tris[2-(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxyethyl)]isocyanurate.

The above-mentioned polymerizable monomer of the present invention canbe prepared by the following procedure: A diol or a triol is allowed toreact with 3-isopropenyl-α,α-dimethylbenzyl isocyanate,4-isopropenyl-α,α-dimethylbenzyl isocyanate or a mixture thereof in theabsence or in the presence of a solvent and in the absence or in thepresence of a catalyst at a suitable temperature.

Exemplary suitable diols include ethylene glycol, 1,3-propanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-propanediol,1,3-butanediol, 2,3-butanediol, 2,5-hexanediol, diethylene glycol,neopentyl glycol, 3-methyl-1,5-pentanediol, dipropylene glycol,triethylene glycol, 1,2-butanediol, 2-ethyl-1,3-hexanediol,3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane,1,4-cyclohexanediol, tricyclo[5,2,1,0²,6 ]decane-4,8-dimethanol,3-chloro-1,2-propanediol, 3-bromo-1,2-propanediol,2,3-dibromo-1,4-butanediol and dibromoneopentyl glycol. Exemplarysuitable triols include triglycerol, trimethylolethane,trimethylolpropane, 1,2,4-butanetriol and1,3,5-tris(2-hydroxyethyl)cyanuric acid. In this reaction, the amount ofthe 3-isopropenyl-α,α-dimethylbenzyl isocyanate,4-isopropenyl-α,α-dimethylbenzyl isocyanate or a mixture thereof ispreferably from 0.8 to 1.1 equivalents, more preferably 0.95 to 1.05equivalents per equivalent of the hydroxyl group in the diol or thetriol. Furthermore, examples of the suitable solvent include hexane,chloroform, benzene, toluene and xylene which are not reactive with theraw materials. The above-mentioned suitable catalyst is a catalyst toaccelerate a urethane formation reaction such as dibutyltin dilaurateand the like. The catalyst is preferably employed in an amount of from0.01 to 5% by weight, preferably from 0.1 to 3% by weight based on theweight of the isocyanate. The suitable reaction temperature ispreferably from about 30° to 200° C., more preferably from 50° to 150°C. After completion of the reaction, the resulting reaction solution isthen purified by column chromatography or another means, therebyobtaining the desired polymerizable monomer of the present invention.

The resin of the present invention has a high surface hardness and isexcellent in transparency, chemical resistance and heat resistance. Inaddition, it is also excellent in workability such as cutting owing tothe high surface hardness.

Moreover, in the preparation of the resin of the present invention,polymerization control in the polymerization step is very easy, andtherefore any peeling, whiting and cracking do not occur in the moldingpolymerization. The resin of the present invention exhibits very goodmoldability and therefore accurate molding is possible.

Thus , the resin of the present invention can be suitably used as aglazing material, a protective cover for display devices, an opticallens and a hard coat material.

Furthermore, when the novel polymerizable monomer of the presentinvention is copolymerized with a monomer having a polymerizable groupin which the polymarization rate is high, for example, an acrylic group,a methacrylic group or a vinylphenyl group, a transparent resin can beobtained which has a high surface hardness and which is excellent inheat resistance and workability such as cutting. Additionally, in thepolymerization step, polymerization control is very easy. Therefore, themonomer of the present invention is useful as the raw material of theabove-mentioned high-hardness transparent resin.

The present invention will be further clarified by the followingexamples, which are intended to be purely exemplary of the invention.

EXAMPLES

In the following examples, part and parts are by weight, unlessotherwise specified.

EXAMPLE 1

6.2 parts of ethylene glycol, 30 parts of toluene, 40.3 parts of3-isopropenyl-α,α-dimethylbenzyl isocyanate and 0.2 part of dibutyltindilaurate were mixed. The solution was then stirred for 1 hour, whilethe temperature of the solution was maintained at 80° C., to carry outthe reaction. After completion of the reaction, the reaction solutionwas concentrated. The resulting concentrate was then purified bychromatography, thereby obtaining 40.0 parts of1,2-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]ethane in theform of colorless transparent liquid.

Values of elemental analysis (as C₂₈ H₃₆ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  72.13         7.59   6.21                                          Calcd. (%) 72.39         7.81   6.03                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR34##                                                                     ##STR35##                                                                     ##STR36##                                                                     ##STR37##                                                                     ##STR38##                                                                     ##STR39##                                                                     ##STR40##                                                                     ##STR41##                                                                    ______________________________________                                    

EXAMPLE 2

6.2 parts of ethylene glycol, 30 parts of toluene, 40.3 parts of4-iospropenyl-α,α-dimethylbenzyl isocyanate and 0.2 part of dibutyltindilaurate were mixed. The mixed solution was then stirred for 1 hour,while the temperature of the solution was maintained at 80° C., to carryout the reaction. After completion of the reaction, the reactionsolution was concentrated. The concentrated solution was then purifiedby chromatography, thereby obtaining 41.2 parts of1,2-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]ethane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₂₈ H₃₆ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  72.59         7.92   6.18                                          Calcd. (%) 72.39         7.81   6.03                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR42##                                                                     ##STR43##                                                                     ##STR44##                                                                     ##STR45##                                                                     ##STR46##                                                                     ##STR47##                                                                     ##STR48##                                                                    ______________________________________                                    

EXAMPLE 3

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 7.6 parts of 1,3-propanediol, therebyobtaining 42.5 parts of1,3-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-propane in theform of a colorless transparent liquid.

Values of elemental analysis (as (C₂₉ H₃₈ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  72.71         7.81   5.69                                          Calcd. (%) 72.77         8.00   5.85                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR49##                                                                     ##STR50##                                                                     ##STR51##                                                                     ##STR52##                                                                     ##STR53##                                                                     ##STR54##                                                                     ##STR55##                                                                     ##STR56##                                                                    ______________________________________                                    

EXAMPLE 4

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 7.6 parts of 1,3-propanediol, therebyobtaining 41.7 parts of1,3-bis[N-(4-isopropenyl-α,≢-dimethylbenzyl)carbamoyloxy]-propane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₂₉ H₃₈ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  72.98         8.13   5.53                                          Calcd. (%) 72.77         8.00   5.85                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR57##                                                                     ##STR58##                                                                     ##STR59##                                                                     ##STR60##                                                                     ##STR61##                                                                     ##STR62##                                                                     ##STR63##                                                                    ______________________________________                                    

EXAMPLE 5

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 9.0 parts of 1,4-butanediol, therebyobtaining 44.4 parts of1,4-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-butane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₀ H₄₀ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  72.88         8.23   5.47                                          Calcd. (%) 73.14         8.18   5.69                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR64##                                                                     ##STR65##                                                                     ##STR66##                                                                     ##STR67##                                                                     ##STR68##                                                                     ##STR69##                                                                     ##STR70##                                                                     ##STR71##                                                                    ______________________________________                                    

EXAMPLE 6

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 9.0 parts of 1,4-butanediol, therebyobtaining 43.9 parts of1,4-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-butane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₀ H₄₀ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  73.29         7.96   5.73                                          Calcd. (%) 73.14         8.18   5.69                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR72##                                                                     ##STR73##                                                                     ##STR74##                                                                     ##STR75##                                                                     ##STR76##                                                                     ##STR77##                                                                     ##STR78##                                                                    ______________________________________                                    

EXAMPLE 7

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 10.4 parts of 1,5-pentanediol, therebyobtaining 44.6 parts of1,5-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-pentane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₁ H₄₂ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  73.53         8.47   5.36                                          Calcd. (%) 73.49         8.35   5.53                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR79##                                                                     ##STR80##                                                                     ##STR81##                                                                     ##STR82##                                                                     ##STR83##                                                                     ##STR84##                                                                     ##STR85##                                                                     ##STR86##                                                                    ______________________________________                                    

EXAMPLE 8

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 10.4 parts of 1,5-pentanediol, therebyobtaining 43.6 parts of1,5-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-pentane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₁ H₄₂ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  73.88         8.19   5.74                                          Calcd. (%) 73.49         8.35   5.53                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR87##                                                                     ##STR88##                                                                     ##STR89##                                                                     ##STR90##                                                                     ##STR91##                                                                     ##STR92##                                                                     ##STR93##                                                                    ______________________________________                                    

EXAMPLE 0

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 11.8 parts of 1,6-hexanediol, therebyobtaining 48.5 parts of1,6-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-hexane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₂ H₄₄ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  73.98         8.43   5.51                                          Calcd. (%) 73.81         8.52   5.38                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR94##                                                                     ##STR95##                                                                     ##STR96##                                                                     ##STR97##                                                                     ##STR98##                                                                     ##STR99##                                                                     ##STR100##                                                                    ##STR101##                                                                   ______________________________________                                    

EXAMPLE 10

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 11.8 parts of 1,6-hexanediol, therebyobtaining 47.7 parts of1,6-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]-hexane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₂ H₄₄ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  73.97         8.61   5.14                                          Calcd. (%) 73.81         8.52   5.38                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR102##                                                                    ##STR103##                                                                    ##STR104##                                                                    ##STR105##                                                                    ##STR106##                                                                    ##STR107##                                                                    ##STR108##                                                                   ______________________________________                                    

EXAMPLE 11

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 7.6 parts of 1,2-propanediol, therebyobtaining 43.1 parts of 1,2-bis[N-(3-isopropenyl-β,β-dimethylbenzyl)carbamoyloxy]propane in the form of a colorlesstransparent liquid.

Values of elemental analysis (as C₂₉ H₃₈ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  72.63         8.15   5.67                                          Calcd. (%) 72.77         8.00   5.85                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR109##                                                                    ##STR110##                                                                    ##STR111##                                                                    ##STR112##                                                                    ##STR113##                                                                    ##STR114##                                                                    ##STR115##                                                                    ##STR116##                                                                    ##STR117##                                                                   ______________________________________                                    

EXAMPLE 12

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 7.6 parts of 1,2-propanediol, therebyobtaining 44.8 parts of 1,2-bis[N-(4-isopropenyl-60,α-dimethylbenzyl)carbamoyloxy]propane in the form of a colorlesstransparent liquid.

Values of elemental analysis (as C₂₉ H₃₈ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  72.69         8.15   5.72                                          Calcd. (%) 72.77         8.00   5.85                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR118##                                                                    ##STR119##                                                                    ##STR120##                                                                    ##STR121##                                                                    ##STR122##                                                                    ##STR123##                                                                    ##STR124##                                                                    ##STR125##                                                                   ______________________________________                                    

EXAMPLE 13

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 9.0 parts of 1,3-butanediol, therebyobtaining 45.2 parts of1,3-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₀ H₄₀ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  72.98         7.87   5.81                                          Calcd. (%) 73.14         8.18   5.69                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR126##                                                                    ##STR127##                                                                    ##STR128##                                                                    ##STR129##                                                                    ##STR130##                                                                    ##STR131##                                                                    ##STR132##                                                                    ##STR133##                                                                    ##STR134##                                                                    ##STR135##                                                                   ______________________________________                                    

EXAMPLE 14

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 9.0 parts of 1,3-butanediol, therebyobtaining 46.7 parts of1,3-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₀ H₄₀ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  73.37         8.03   5.86                                          Calcd. (%) 73.14         8.18   5.69                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR136##                                                                    ##STR137##                                                                    ##STR138##                                                                    ##STR139##                                                                    ##STR140##                                                                    ##STR141##                                                                    ##STR142##                                                                    ##STR143##                                                                    ##STR144##                                                                   ______________________________________                                    

EXAMPLE 15

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 9.0 parts of 2,3-butanediol, therebyobtaining 44.8 parts of2,3-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₀ H₄₀ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  73.01         8.29   5.42                                          Calcd. (%) 73.14         8.18   5.69                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR145##                                                                    ##STR146##                                                                    ##STR147##                                                                    ##STR148##                                                                    ##STR149##                                                                    ##STR150##                                                                    ##STR151##                                                                    ##STR152##                                                                    ##STR153##                                                                   ______________________________________                                    

EXAMPLE 16

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 9.0 parts of 2,3-butanediol, therebyobtaining 42.9 parts of2,3-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₀ H₄₀ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  73.44         8.09   5.47                                          Calcd. (%) 73.14         8.18   5.69                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR154##                                                                    ##STR155##                                                                    ##STR156##                                                                    ##STR157##                                                                    ##STR158##                                                                    ##STR159##                                                                    ##STR160##                                                                    ##STR161##                                                                   ______________________________________                                    

EXAMPLE 17

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 11.8 parts of 2,5-hexanediol, therebyobtaining 49.1 parts of2,5-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]hexane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₂ H₄₄ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  73.98         8.36   5.14                                          Calcd. (%) 73.81         8.52   5.38                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                      δ = 0.85˜1.75 (m, 22H,                                             ##STR162##                                                                    ##STR163##                                                                    ##STR164##                                                                    ##STR165##                                                                    ##STR166##                                                                    ##STR167##                                                                    ##STR168##                                                                    ##STR169##                                                                   ______________________________________                                    

EXAMPLE 18

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 11.8 parts of 2,5-hexanediol, therebyobtaining 47.9 parts of2,5-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]hexane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₂ H₄₄ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  74.03         8.77   5.28                                          Calcd. (%) 73.81         8.52   5.38                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                      δ = 0.85˜1.75 (m, 22H,                                             ##STR170##                                                                    ##STR171##                                                                    ##STR172##                                                                    ##STR173##                                                                    ##STR174##                                                                    ##STR175##                                                                    ##STR176##                                                                   ______________________________________                                    

EXAMPLE 19

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 10.0 parts of diethylene glycol,thereby obtaining 47.4 parts ofbis[2-(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethyl]ether inthe form of a colorless transparent liquid.

Values of elemental analysis (as C₃₀ H₄₀ N₂ O₅)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  70.66         7.72   5.68                                          Calcd. (%) 70.84         7.93   5.51                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR177##                                                                    ##STR178##                                                                    ##STR179##                                                                    ##STR180##                                                                    ##STR181##                                                                    ##STR182##                                                                    ##STR183##                                                                    ##STR184##                                                                    ##STR185##                                                                   ______________________________________                                    

EXAMPLE 20

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 10.6 parts of diethylene glycol,thereby obtaining 47.6 parts ofbis[2-(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethyl] ether inthe form of a colorless transparent liquid.

Values of elemental analysis (as C₃₀ H₄₀ N₂ O₅)

    ______________________________________                                                   C            H      N                                              ______________________________________                                        Found (%)  70.79        7.98   5.38                                           Calcd. (%) 70.84        7.93   5.51                                           ______________________________________                                         NMR(δ/CDCl.sub.3)                                                       ##STR186##                                                                    ##STR187##                                                                    ##STR188##                                                                    ##STR189##                                                                    ##STR190##                                                                    ##STR191##                                                                    ##STR192##                                                                    ##STR193##                                                               

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 10.4 parts of neopentyl glycol,thereby obtaining 46.9 parts of2,2-dimethyl-1,3-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₃₁ H₄₂ N₂ O₄)

    ______________________________________                                                   C            H      N                                              ______________________________________                                        Found (%)  73.38        8.34   5.74                                           Calcd. (%) 73.49        8.35   5.53                                           ______________________________________                                         NMR(δ/CDCl.sub.3)                                                       ##STR194##                                                                    ##STR195##                                                                    ##STR196##                                                                    ##STR197##                                                                    ##STR198##                                                                    ##STR199##                                                                    ##STR200##                                                                    ##STR201##                                                                    ##STR202##                                                               

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 10.4 parts of neopentyl glycol,thereby obtaining 48.1 parts of2,2-dimethyl-2,3-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₃₁ H₄₂ N₂ O₄)

    ______________________________________                                                   C            H      N                                              ______________________________________                                        Found (%)  73.18        8.42   5.71                                           Calcd. (%) 73.49        8.35   5.53                                           ______________________________________                                         NMR(δ/CDCl.sub.3)                                                       ##STR203##                                                                    ##STR204##                                                                    ##STR205##                                                                    ##STR206##                                                                    ##STR207##                                                                    ##STR208##                                                                    ##STR209##                                                                    ##STR210##                                                               

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 11.8 parts of3-methyl-1,5-pentanediol, thereby obtaining 47.7 parts of3-methyl-1,5[N-(3-isopropenyl-α, α-dimethylbenzyl)carbamoyloxy]pentanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₃₂ H₄₄ N₂ O₄)

    ______________________________________                                                   C            H      N                                              ______________________________________                                        Found (%)  73.67        8.74   5.36                                           Calcd. (%) 73.81        8.52   5.38                                           ______________________________________                                         NMR(δ/CDCl.sub.3)                                                       ##STR211##                                                                    ##STR212##                                                                    ##STR213##                                                                    ##STR214##                                                                    ##STR215##                                                                    ##STR216##                                                                    ##STR217##                                                                    ##STR218##                                                                    ##STR219##                                                                   ______________________________________                                    

EXAMPLE 24

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 11.8 parts of3-methyl-1,5-pentanediol, thereby obtaining 46.8 parts of3-methyl-1,5-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]pentanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₃₂ H₄₄ N₂ O₄)

    ______________________________________                                                   C            H      N                                              ______________________________________                                        Found (%)  73.93        8.76   5.24                                           Calcd. (%) 73.81        8.52   5.38                                           ______________________________________                                         NMR(δ/CDCl.sub.3)                                                       ##STR220##                                                                    ##STR221##                                                                    ##STR222##                                                                    ##STR223##                                                                    ##STR224##                                                                    ##STR225##                                                                    ##STR226##                                                                    ##STR227##                                                               

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 13.4 parts of dipropylene glycol,thereby obtaining 49.7 parts ofbis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)isopropyl ] etherin the form of a colorless transparent liquid.

Values of elemental analysis (as (C₃₂ H₄₄ N₂ O₅)

    ______________________________________                                                   C            H      N                                              ______________________________________                                        Found (%)  71.78        8.14   5.06                                           Calcd. (%) 71.61        8.26   5.22                                           ______________________________________                                         NMR(δ/CDCl.sub.3)                                                       ##STR228##                                                                    ##STR229##                                                                    ##STR230##                                                                    ##STR231##                                                                    ##STR232##                                                                    ##STR233##                                                                    ##STR234##                                                                    ##STR235##                                                                    ##STR236##                                                                    ##STR237##                                                                   or                                                                             ##STR238##                                                                    ##STR239##                                                                    ##STR240##                                                                    ##STR241##                                                                    ##STR242##                                                                    ##STR243##                                                                    ##STR244##                                                                    ##STR245##                                                                    ##STR246##                                                                    ##STR247##                                                                   or                                                                             ##STR248##                                                                    ##STR249##                                                                    ##STR250##                                                                    ##STR251##                                                                    ##STR252##                                                                    ##STR253##                                                                    ##STR254##                                                                    ##STR255##                                                                    ##STR256##                                                                    ##STR257##                                                                    ##STR258##                                                               

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 13.4 parts of dipropylene glycol,thereby obtaining 50.6 parts ofbis[(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)isopropyl] etherin the form of a colorless transparent liquid (a mixture of isomers).

Values of elemental analysis (as C₃₂ H₄₄ N₂ O₅)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  71.77         8.05   5.38                                          Calcd. (%) 71.61         8.26   5.22                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR259##                                                                    ##STR260##                                                                    ##STR261##                                                                    ##STR262##                                                                    ##STR263##                                                                    ##STR264##                                                                    ##STR265##                                                                    ##STR266##                                                                    ##STR267##                                                                    ##STR268##                                                                    ##STR269##                                                                    ##STR270##                                                                    ##STR271##                                                                    ##STR272##                                                                    ##STR273##                                                                    ##STR274##                                                                    ##STR275##                                                                    ##STR276##                                                                    ##STR277##                                                                    ##STR278##                                                                    ##STR279##                                                                    ##STR280##                                                                    ##STR281##                                                                    ##STR282##                                                                    ##STR283##                                                                    ##STR284##                                                                    ##STR285##                                                                    ##STR286##                                                                   ______________________________________                                    

EXAMPLE 27

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 15.0 parts of triethylene glycol,thereby obtaining 49.5 parts ofbis[2-(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethoxy]ethane inthe form of a colorless transparent liquid.

Values of elemental analysis (as C₃₂ H₄₄ N₂ O₆)

    ______________________________________                                                    C            H      N                                             ______________________________________                                        Found (%)   69.62        8.31   4.93                                          Calcd. (%)  69.54        8.02   5.07                                          ______________________________________                                        NMR(δ/CDCl.sub.3)                                                        ##STR287##                                                                    ##STR288##                                                                    ##STR289##                                                                    ##STR290##                                                                    ##STR291##                                                                    ##STR292##                                                                    ##STR293##                                                                    ##STR294##                                                                    ##STR295##                                                                   ______________________________________                                    

EXAMPLE 28

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 15.0 parts of triethylene glycol,thereby obtaining 51.5 parts ofbis[2-(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethoxy]ethane inthe form of a colorless transparent liquid.

Values of elemental analysis (as C₃₂ H₄₄ N₂ O₆)

    ______________________________________                                                    C            H      N                                             ______________________________________                                        Found (%)   69.61        8.29   5.09                                          Calcd. (%)  69.54        8.02   5.07                                          ______________________________________                                        NMR(δ/CDCl.sub.3)                                                        ##STR296##                                                                    ##STR297##                                                                    ##STR298##                                                                    ##STR299##                                                                    ##STR300##                                                                    ##STR301##                                                                    ##STR302##                                                                    ##STR303##                                                                   ______________________________________                                    

EXAMPLE 29

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 9.0 parts of 1,2-butanediol, therebyobtaining 43.4 parts of1,2-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₀ H₄₀ N₂ O₄)

    ______________________________________                                                    C            H      N                                             ______________________________________                                        Found (%)   72.98        8.34   5.47                                          Calcd. (%)  73.14        8.18   5.69                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR304##                                                                    ##STR305##                                                                    ##STR306##                                                                    ##STR307##                                                                    ##STR308##                                                                    ##STR309##                                                                    ##STR310##                                                                    ##STR311##                                                                    ##STR312##                                                                   ______________________________________                                    

EXAMPLE 30

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 9.0 parts of 1,2-butanediol, therebyobtaining 46.4 parts of1,2-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane in theform of a colorless transparent liquid.

Values of elemental analysis (as C₃₀ H₄₀ N₂ O₄)

    ______________________________________                                                    C            H      N                                             ______________________________________                                        Found (%)   73.18        8.07   5.43                                          Calcd. (%)  73.14        8.18   5.69                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR313##                                                                    ##STR314##                                                                    ##STR315##                                                                    ##STR316##                                                                    ##STR317##                                                                    ##STR318##                                                                    ##STR319##                                                                    ##STR320##                                                                   ______________________________________                                    

EXAMPLE 31

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 14.6 parts of 2-ethyl-1,3-hexanediol,thereby obtaining 50.4 parts of2-ethyl-1,3-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]hexanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₃₄ H₄₈ N₂ O₄)

    ______________________________________                                                    C            H      N                                             ______________________________________                                        Found (%)   74.56        8.77   5.04                                          Calcd. (%)  74.42        8.82   5.10                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR321##                                                                    ##STR322##                                                                    ##STR323##                                                                    ##STR324##                                                                    ##STR325##                                                                    ##STR326##                                                                    ##STR327##                                                                    ##STR328##                                                                    ##STR329##                                                                   ______________________________________                                    

EXAMPLE 32

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 14.6 parts of 2-ethyl-1,3-hexanediol,thereby obtaining 51.1 parts of2-ethyl-1,3-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]hexanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₃₄ H₄₈ N₂ O₄)

    ______________________________________                                                    C            H      N                                             ______________________________________                                        Found (%)   74.47        8.73   5.16                                          Calcd. (%)  74.42        8.82   5.10                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR330##                                                                    ##STR331##                                                                    ##STR332##                                                                    ##STR333##                                                                    ##STR334##                                                                    ##STR335##                                                                    ##STR336##                                                                    ##STR337##                                                                   ______________________________________                                    

EXAMPLE 33

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 30.4 parts of3,9-bis(1,1-dimethyl-2-hydroxyethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane,thereby obtaining 66.7 parts of3,9-bis[1,1-dimethyl-2-(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy(ethyl]-2,4,8,10-tetraoxaspiro(5,5)undecanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₄₁ H₅₈ N₂ O₈)

    ______________________________________                                                    C            H      N                                             ______________________________________                                        Found (%)   69.56        8.34   3.72                                          Calcd. (%)  69.66        8.27   3.96                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR338##                                                                    ##STR339##                                                                    ##STR340##                                                                    ##STR341##                                                                    ##STR342##                                                                    ##STR343##                                                                    ##STR344##                                                                    ##STR345##                                                                    ##STR346##                                                                    ##STR347##                                                                   ______________________________________                                    

EXAMPLE 34

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 30.4 parts of3,9-bis(1,1-dimethyl-2-hydroxyethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane,thereby obtaining 63.4 parts of3,9-bis[1,1-dimethyl-2-(N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy(ethyl]-2,4,8,10-tetraoxaspiro(5,5)undecanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₄₁ H₅₈ N₂ O₈)

    ______________________________________                                                    C            H      N                                             ______________________________________                                        Found (%)   69.73        8.48   3.75                                          Calcd. (%)  69.66        8.27   3.96                                          ______________________________________                                        NMR(δ/CDCl.sub.3)                                                        ##STR348##                                                                    ##STR349##                                                                    ##STR350##                                                                    ##STR351##                                                                    ##STR352##                                                                    ##STR353##                                                                    ##STR354##                                                                    ##STR355##                                                                    ##STR356##                                                                   ______________________________________                                    

EXAMPLE 35

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 11.6 parts of 1,4-cyclohexanediol,thereby obtaining 48.2 parts of1,4-bis[N-(3-isopropenyl-α,≢-dimethylbenzyl)carbamoyloxy]cyclohexane inthe form of a colorless transparent liquid.

Values of elemental analysis (as C₃₂ H₄₂ N₂ O₄)

    ______________________________________                                                    C            H      N                                             ______________________________________                                        Found (%)   74.23        8.05   5.62                                          Calcd. (%)  74.10        8.16   5.40                                          ______________________________________                                        NMR(δ/CDCl.sub.3)                                                        ##STR357##                                                                    ##STR358##                                                                    ##STR359##                                                                    ##STR360##                                                                    ##STR361##                                                                    ##STR362##                                                                    ##STR363##                                                                   ______________________________________                                    

EXAMPLE 36

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 11.6 parts of 1,4-cyclohexanediol,thereby obtaining 46.7 parts of1,4-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]cyclohexane inthe form of a colorless transparent liquid.

Values of elemental analysis (as C₃₂ H₄₂ N₂ O₄)

    ______________________________________                                                    C            H      N                                             ______________________________________                                        Found (%)   74.35        8.32   5.29                                          Calcd. (%)  74.10        8.16   5.40                                          ______________________________________                                        NMR(δ/CDCl.sub.3)                                                        ##STR364##                                                                    ##STR365##                                                                    ##STR366##                                                                    ##STR367##                                                                    ##STR368##                                                                    ##STR369##                                                                    ##STR370##                                                                   ______________________________________                                    

EXAMPLE 37

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 19.6 parts of tricyclo[5,2,1,0²,6]decane-4,8-dimethanol, thereby obtaining 55.9 parts of4,8-bis[N-(3-isopropenyl-α,α-dimethylbezyl)carbamoyloxymethyl]tricyclo]5,2,1,0²,6]decane in the form of a colorless transparent liquid.

Values of elemental analysis (as C₃₈ H₅₀ N₂ O₄)

    ______________________________________                                                    C            H      N                                             ______________________________________                                        Found (%)   76.27        8.69   4.55                                          Calcd. (%)  76.22        8.42   4.68                                          ______________________________________                                        NMR(δ/CDl.sub.3)                                                         ##STR371##                                                                    ##STR372##                                                                    ##STR373##                                                                    ##STR374##                                                                    ##STR375##                                                                    ##STR376##                                                                    ##STR377##                                                                   ______________________________________                                    

EXAMPLE 38

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 19.6 parts of tricyclo[5,2,1,0²,6]decane-4,8-dimethanol, thereby obtaining 54.8 parts of4,8-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoylmethyl]tricyclo[5,2,1,0²,6]decane in the form of a colorless transparent liquid.

Values of elemental analysis (as C₃₈ H₅₀ N₂ O₄)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  76.19         8.65   4.32                                          Calcd. (%) 76.22         8.42   4.68                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR378##                                                                    ##STR379##                                                                    ##STR380##                                                                    ##STR381##                                                                    ##STR382##                                                                    ##STR383##                                                                    ##STR384##                                                                   ______________________________________                                    

EXAMPLE 39

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 11.1 parts of3-chloro-1,2-propanediol, thereby obtaining 49.2 parts of3-chloro-1,2-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₂₉ H₃₇ N₂ O₄ Cl)

    ______________________________________                                                     C      H          N    Cl                                        ______________________________________                                        Found (%)    67.72  7.31       5.35 6.98                                      Calcd. (%)   67.89  7.27       5.46 6.91                                      ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR385##                                                                    ##STR386##                                                                    ##STR387##                                                                    ##STR388##                                                                    ##STR389##                                                                    ##STR390##                                                                    ##STR391##                                                                    ##STR392##                                                                   ______________________________________                                    

EXAMPLE 40

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 11.1 parts of3-chloro-1,2-propanediol, thereby obtaining 49.8 parts of3-chloro-1,2-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₂₉ H₃₇ N₂ O₄ Cl)

    ______________________________________                                                     C      H          N    Cl                                        ______________________________________                                        Found (%)    68.04  7.31       5.24 6.83                                      Calcd. (%)   67.89  7.27       5.46 6.91                                      ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR393##                                                                    ##STR394##                                                                    ##STR395##                                                                    ##STR396##                                                                    ##STR397##                                                                    ##STR398##                                                                    ##STR399##                                                                   ______________________________________                                    

EXAMPLE 41

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 15.5 parts of 3-bromo-1,2-propanediol,thereby obtaining 51.4 parts of3-bromo-1,2-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₂₉ H₃₇ N₂ O₄ Br)

    ______________________________________                                                     C      H          N    Br                                        ______________________________________                                        Found (%)    62.31  6.49       5.21 14.08                                     Calcd. (%)   62.48  6.69       5.02 14.33                                     ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR400##                                                                    ##STR401##                                                                    ##STR402##                                                                    ##STR403##                                                                    ##STR404##                                                                    ##STR405##                                                                    ##STR406##                                                                    ##STR407##                                                                   ______________________________________                                    

EXAMPLE 42

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced wit 15.5 parts of 3-bromo-1,2-propanediol,thereby obtaining 52.3 parts of3-bromo-1,2-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₂₉ H₃₇ N₂ O₄ Br)

    ______________________________________                                                     C      H          N  Br                                          ______________________________________                                        Found (%)    62.29  6.81       5.13                                                                             14.15                                       Calcd. (%)   62.48  6.69       5.02                                                                             14.33                                       ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR408##                                                                    ##STR409##                                                                    ##STR410##                                                                    ##STR411##                                                                    ##STR412##                                                                    ##STR413##                                                                    ##STR414##                                                                   ______________________________________                                    

EXAMPLE 43

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 24.8 parts of2,3-dibromo-1,4-butanediol, thereby obtaining 59.8 parts of2,3-dibromo-1,4-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₃₀ H₃₈ N₂ O₄ Br₂)

    ______________________________________                                                     C      H          N    Br                                        ______________________________________                                        Found (%)    55.58  5.93       4.25 24.79                                     Calcd. (%)   55.40  5.89       4.31 24.57                                     ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR415##                                                                    ##STR416##                                                                    ##STR417##                                                                    ##STR418##                                                                    ##STR419##                                                                    ##STR420##                                                                    ##STR421##                                                                    ##STR422##                                                                   ______________________________________                                    

EXAMPLE 44

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 24.8 parts of2,3-dibromo-1,4-butanediol, thereby obtaining 57.6 parts of2,3-dibromo-1,4-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₃₀ H₃₈ N₂ O₄ Br₂)

    ______________________________________                                                     C      H          N    Br                                        ______________________________________                                        Found (%)    55.28  5.69       4.53 24.72                                     Calcd. (%)   55.40  5.89       4.31 24.57                                     ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR423##                                                                    ##STR424##                                                                    ##STR425##                                                                    ##STR426##                                                                    ##STR427##                                                                    ##STR428##                                                                    ##STR429##                                                                   ______________________________________                                    

EXAMPLE 45

The same procedure as in Example 1 was repeated except that 6.2 parts ofethylene glycol was replaced with 26.2 parts of dibromoneopentyl glycol,thereby obtaining 62.1 parts of2,2-dibromomethyl-1,3-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₃₁ H₄₀ N₂ O₄ Br₂)

    ______________________________________                                                     C      H          N    Br                                        ______________________________________                                        Found (%)    55.93  6.14       4.18 24.00                                     Calcd. (%)   56.04  6.07       4.22 24.05                                     ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR430##                                                                    ##STR431##                                                                    ##STR432##                                                                    ##STR433##                                                                    ##STR434##                                                                    ##STR435##                                                                    ##STR436##                                                                   ______________________________________                                    

EXAMPLE 46

The same procedure as in Example 2 was repeated except that 6.2 parts ofethylene glycol was replaced with 26.2 parts of dibromoneopentyl glycol,thereby obtaining 63.2 parts of2,2-dibromomethyl-1,3-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₃₁ H₄₀ N₂ O₄ Br₂)

    ______________________________________                                                     C      H          N    Br                                        ______________________________________                                        Found (%)    56.21  6.03       4.39 24.32                                     Calcd. (%)   56.04  6.07       4.22 24.05                                     ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR437##                                                                    ##STR438##                                                                    ##STR439##                                                                    ##STR440##                                                                    ##STR441##                                                                    ##STR442##                                                               

6.1 parts of glycerol, 30 parts of toluene, 40.3 parts of3-isopropenyl-α,α-dimethylbenzyl isocyanate and 0.2 part of dibutyltindilaurate were mixed. The solution was then stirred for 1 hour, whilethe temperature of the solution was maintained at 90° C., to carry outthe reaction. After completion of the reaction, the reaction solutionwas concentrated. The resulting concentrate was then purified bychromatography, thereby obtaining 42.4 parts of1,2,3-tris[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propane.

Values of elemental analysis (as C₄₂ H₅₃ N₃ O₆)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  72.26         7.71   6.09                                          Calcd. (%) 72.49         7.68   6.04                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR443##                                                                    ##STR444##                                                                    ##STR445##                                                                    ##STR446##                                                                    ##STR447##                                                                    ##STR448##                                                                    ##STR449##                                                                    ##STR450##                                                               

6.1 parts of glycerol, 30 parts of toluene, 26.8 parts of3-isopropenyl-α,α-dimethylbenzyl isocyanate and 0.2 part of dibutyltindilaurate were mixed. The solution was then stirred for 1 hour, whilethe temperature of the solution was maintained at 60° C. Afterward, 13.4parts of 4-isopropenyl-α,α-dimethylbenzyl isocyanate was added thereto,and the solution was stirred for 1 hour, maintaining the temperature ofthe solution at 80° C., to carry out reaction. After completion of thereaction, the reaction solution was concentrated. The resultingconcentrate was then purified by chromatography, thereby obtaining 41.3parts of 1,3-bis[N-(3-isopropenyl- , -dimethylbenzyl)carbamoyloxy]-2-[N-4-isopropenyl- , -dimethylbenzyl)carbamoyloxy]propane in the form of a colorlesstransparent liquid.

Values of elemental analysis (as C₄₂ H₅₃ N₃ O₆)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  72.31         7.74   6.17                                          Calcd. (%) 72.49         7.68   6.04                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR451##                                                                    ##STR452##                                                                    ##STR453##                                                                    ##STR454##                                                                    ##STR455##                                                                    ##STR456##                                                                    ##STR457##                                                                     EXAMPLE 49 The same procedure as in Example 47 was repeated except that     .1 parts of ethylene glycol was replaced with 8.0 parts of                    trimethylolethane, thereby obtaining 44.5 parts of 1,1,1-tris[N-(3-isoprop    enyl-α,α-dimethylbenzyl)carbamoyloxymethyl]ethane in the form 

Values of elemental analysis (as C₄₄ H₅₇ N₃ O₆)

    ______________________________________                                                    C            H      N                                             ______________________________________                                        Found (%)   72.87        7.98   5.75                                          Calcd. (%)  73.00        7.94   5.80                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR458##                                                                    ##STR459##                                                                    ##STR460##                                                                    ##STR461##                                                                    ##STR462##                                                                    ##STR463##                                                                    ##STR464##                                                                    ##STR465##                                                                   ______________________________________                                    

EXAMPLE 50

The same procedure as in Example 47 was repeated except that 6.1 partsof glycerol was replaced with 8.9 parts of trimethylolpropane, therebyobtaining 42.7 parts of2-ethyl-2-[N-(3-isopropenyl-α,αdimethylbenzyl)carbamoyloxymethyl]-1,3-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₄₅ H₅₉ N₃ O₆)

    ______________________________________                                                    C            H      N                                             ______________________________________                                        Found (%)   73.06        8.14   5.65                                          Calcd. (%)  73.24        8.06   5.69                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR466##                                                                    ##STR467##                                                                    ##STR468##                                                                    ##STR469##                                                                    ##STR470##                                                                    ##STR471##                                                                    ##STR472##                                                                    ##STR473##                                                                   ______________________________________                                    

EXAMPLE 51

8.9 parts of trimethylolpropane, 30 parts of toluene, 13.4 parts of3-isopropenyl-α,α-dimethylbenzyl isocyanate, 26.8 parts of4-isopropenyl-α,α-dimethylbenzyl isocyanate and 0.2 part of dibutyltindilaurate were mixed. The solution was the stirred for 1 hour, while thetemperature of the solution was maintained at 80° C., to carry out thereaction. After completion of the reaction, the reaction solution wasconcentrated. The resulting concentrate was then purified bychromatography, thereby obtaining 43.5 parts of2-ethyl-2-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]-1,3-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propanein the form of a colorless transparent liquid.

Values of elemental analysis (as C₄₅ H₅₉ N₃ O₆)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  73.17         8.04   5.73                                          Calcd. (%) 73.24         8.06   5.69                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR474##                                                                    ##STR475##                                                                    ##STR476##                                                                    ##STR477##                                                                    ##STR478##                                                                    ##STR479##                                                                    ##STR480##                                                               

The same procedure as in Example 47 was repeated except that 6.1 partsof glycerol was replaced with 7.1 parts of 1,2,4-butanetriol, therebyobtaining 41.8 parts of1,2,4-tris]N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]butane inthe form of a colorless transparent liquid.

Values of elemental analysis (as C₄₃ H₅₅ N₃ O₆)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  72.81         7.79   5.96                                          Calcd. (%) 72.75         7.81   5.92                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR481##                                                                    ##STR482##                                                                    ##STR483##                                                                    ##STR484##                                                                    ##STR485##                                                                    ##STR486##                                                                    ##STR487##                                                                    ##STR488##                                                                    ##STR489##                                                               

The same procedure as in Example 47 was repeated except that 6.1 partsof glycerol was replaced with 17.4 parts of1,3,5-tris(2-hydroxyethyl)cyanuric acid. The reaction solution wasmaintained under toluene reflux, thereby obtaining 49.9 parts of1,3,5-tris[2-(N-(3-isopropenyl- ,-dimethylbenzyl)-carbamoyloxyethyl)]isocyanurate in the form of acolorless transparent liquid.

Values of elemental analysis (as C₄₈ H₆₀ N₆ O₉)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  66.73         6.87   9.81                                          Calcd. (%) 66.65         6.99   9.72                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR490##                                                                    ##STR491##                                                                    ##STR492##                                                                    ##STR493##                                                                    ##STR494##                                                                    ##STR495##                                                                    ##STR496##                                                                    ##STR497##                                                                    ##STR498##                                                               

17.4 parts of 1,3,5-tris(2-hydroxyethyl)cyanuric acid, 30 parts oftoluene, 26.8 parts of 3-isopropenyl-α,α-dimethylbenzyl isocyanate, 13.4parts of 4-isopropenyl-α,α-dimethylbenzyl isocyanate and 0.2 part ofdibutyltin dilaurate were mixed. The solution was then stirred for 1hour under reflux, to carry out reaction. After completion of thereaction, the reaction solution was concentrated. The resultingconcentrate was then purified by chromatography, thereby obtaining 51.4parts of1,3-bis[2-[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxyethyl]]-5-[2-[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxyethyl]]isocyanurate in the form of a colorless transparent liquid.

Values of elemental analysis (as C₄₈ H₆₀ N₆ O₉)

    ______________________________________                                                   C             H      N                                             ______________________________________                                        Found (%)  66.58         7.05   9.63                                          Calcd. (%) 66.65         6.99   9.72                                          ______________________________________                                        NMR (δ/CDCl.sub.3)                                                       ##STR499##                                                                    ##STR500##                                                                    ##STR501##                                                                    ##STR502##                                                                    ##STR503##                                                                    ##STR504##                                                                    ##STR505##                                                                    ##STR506##                                                                   In the following examples, the high surface hardness transparent resin of 

201 parts of 3-isopropenyl-α,α-dimethylbenzylisocyanate was mixed with 1part of dibutyltin dilaurate and 100 parts of methanol, and the mixturewas then stirred for 30 minutes under methanol reflux in order to carryout the reaction. After completion of the reaction, methanol wasdistilled off, and the residue was then purified through achromatography, thereby obtaining 198 parts of a colorless liquidmonomer having the following structure: ##STR507##

To 116.7 parts of the monomer thus prepared added 70.6 parts oftris(acryloyloxyethyl) isocyanurate, and they were then mixedsufficiently. Afterward, 1.9 parts of benzoyl peroxide was addedthereto, followed by mixing and defoaming. This solution was then pouredinto a mold prepared by interposing a 5-mm-thick polyvinyl chloridespacer between peripheral portions of two 5-mm-thick glass plates andthen firmly fastening them together with a clamp, and polymerization waseffected in a hot-air oven for polymerization by elevating thetemperature therein from 70° C. to 150° C. over 1.5 hours. Aftercooling, a transparent resin plate having a smooth surface was releasedfrom the mold.

EXAMPLE 56

17.6 parts of pentaerythritol tetraacrylate and 0.3 part of benzoylperoxide were added to 23.2 parts of1,2-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]ethane obtainedby the same procedure as in Example 1, followed by sufficient mixing anddefoaming. The resulting uniformed solution was then poured into a moldprepared by interposing a 5-mm-thick polyvinyl chloride spacer betweenperipheral portions of two 5-mm-thick glass plates and then firmlyfastening them together with a clamp. Polymerization was then effectedin a hot-air oven for polymerization by elevating the temperaturetherein from 70° C. to 150° C. over 1.5 hours. After cooling, atransparent resin plate having a smooth surface was released from themold.

EXAMPLE 57

17.6 parts of pentaerythritol tetraacrylate and 0.3 part of benzoylperoxide were added to 23.2 parts of1,2-bis[N-(4-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]ethane obtainedby the same procedure as in Example 2, followed by sufficient mixing anddefoaming. The resulting uniformed solution was then poured into a moldprepared by interposing a 5-mm-thick polyvinyl chloride spacer betweenperipheral portions of two 5-mm-thick glass plates, and then firmlyfastening them together with a clamp. Polymerization was then effectedin a hot-air oven for polymerization by elevating the temperaturetherein from 70° C. to 150° C. over 1.5 hours. After cooling, atransparent resin plate having a smooth surface was released from themold.

EXAMPLE 58

33.4 parts of trimethylolpropane trimethacrylate and 0.3 part of benzoylperoxide were added to 25.4 parts ofbis[2-(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy)ethyl] etherobtained by the same procedure as in Example 19, followed by sufficientmixing and defoaming. The resulting solution was then poured into a moldprepared by interposing a 5-mm-thick polyvinyl chloride spacer betweenperipheral portions of two 5-mm-thick glass plates and then firmlyfastening them together with a clamp. Polymerization was then effectedin a hot-air oven for polymerization by elevating the temperaturetherein from 70° C. to 150° C. over 1.5 hours. After cooling, atransparent resin plate having a smooth surface was released from themold.

EXAMPLE 59

20.0 parts of ethyl acrylate and 0.3part of benzoyl peroxide were addedto 29.9 parts of4,8-bis[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxymethyl]tricyclo[5,2,1,0²,6]decane obtained by the same procedure as in Example 37, followed bysufficient mixing and defoaming. The resulting uniformed solution wasthen poured into a mold prepared by interposing a 5-mm-thick polyvinylchloride spacer between peripheral portions of two 5-mm-thick glassplates and then firmly fastening them together with a clamp.Polymerization was then effected in a hot-air oven for polymerization byelevating the temperature therein from 70° C. to 150° C. over 1.5 hours.After cooling, a transparent resin plate having a smooth surface wasreleased from the mold.

EXAMPLE 60

26.4 parts of pentaerythritol tetraacrylate and 0.3 part of benzoylperoxide were added to 31.7 parts of1,2,3-tris[N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxy]propaneobtained by the same procedure as in Example 47, followed by sufficientmixing and defoaming. The resulting uniformed solution was then pouredinto a mold prepared by interposing a 5-mm-thick polyvinyl chloridespacer between peripheral portions of two 5-mm-thick glass plates andthen firmly fastening them together with a clamp. Polymerization wasthen effected in a hot-air oven for polymerization by elevating thetemperature therein from 70° C. to 150° C. over 1.5 hours. Aftercooling, a transparent resin plate having a smooth surface was releasedfrom the mold.

EXAMPLE 61

42.3 parts of tris(acryloyloxyethyl)isocyanurate and 0.4 part of benzoylperoxide were added to 43.3 parts of1,3,5-tris[2-(N-(3-isopropenyl-α,α-dimethylbenzyl)carbamoyloxyethyl]isocyanurate obtained by the same procedure as in Example 53, followedby sufficient mixing and defoaming. The resulting solution was thenpoured into a mold prepared by interposing a 5-mm-thick polyvinylchloride spacer between peripheral portions of two 5-mm-thick glassplates and then firmly fastening them together with a clamp.Polymerization was then effected in a hot-air oven for polymerization byelevating the temperature therein from 70° C. to 150° C. over 1.5 hours.After cooling, a transparent resin plate having a smooth surface wasreleased from the mold.

EXAMPLE 62

11.5 parts of glycerol and 0.5 part of dibutyltin dilaurate were addedto 100.6 parts of 3-isopropenyl-α,α-dimethylbenzyl isocyanate, and themixture was then heated with stirring for 1 hour so that an internaltemperature might be 80° C. After cooling, 4.0 parts of methanol wasadded thereto, and heating was then carried out with stirring for 1 hourso that the internal temperature might be 55° C., in order to obtain amixture of two kinds of urethane compounds. To this mixture, 92.0 partsof pentaerythritol tetraacrylate was added, followed by mixing anddefoaming. This solution was then poured into a mold prepared byinterposing a 5-mm-thick polyvinyl chloride spacer between peripheralportions of two 5-mm-thick glass plates and then firmly fastening themtogether with a clamp. Polymerization was then effected in a hot-airoven for polymerization by elevating the temperature therein from 70° C.to 150° C. over 1.5 hours. After cooling, a transparent resin platehaving a smooth surface was released from the mold.

EXAMPLE 63

11.6 parts of ethylene glycol and 0.1 part of dibutyltin dilaurate wereadded to 75.5 parts of 3-isopropenyl-α,α-dimethylbenzyl isocyanate, andthe mixture was then heated with stirring for 1 hour so that an internaltemperature might be 70° C. Afterward, 41.5 parts ofN-(3-isopropenyl-α,α-dimethylbenzyl)-2-methacryloyloxy carbamate wasadded thereto.

88.1 parts of pentaerythritol tetraacrylate and 1.0 part of benzoylperoxide were added thereto, followed by sufficient mixing anddefoaming. The solution was then poured into a mold prepared byinterposing a 5-mm-thick polyvinyl chloride spacer between peripheralportions of two 5-mm-thick glass plates and then firmly fastening themtogether with a clamp. Polymerization was then effected in a hot-airoven for polymerization by elevating the temperature therein from 70° C.to 150° C. over 1.5 hours. After cooling, a transparent resin platehaving a smooth surface was released from the mold.

For the transparent resin plates obtained in Examples 55 to 63, variousphysical properties were measured. The results are set forth in Table 1.

In measuring these physical properties, the following procedures wereemployed:

(1) Appearance: The appearance of each polymer plate was evaluated byobserving the same by the naked eye. The polymer plates which were freefrom cracks and a rough surface were denoted by "O", and the plateshaving such disadvantages were denoted by "X".

(2) Surface Hardness: This was measured by the use of a pencilscratching test machine for coating films under JIS-K-5401.

(3) Heat Resistance: The resin plates were allowed to stand at 120° C.for 4 hours in a hot-air drier. Afterward, the resin plates wereobserved by the naked eye. The plates which were free from coloring andstrain on the surfaces thereof were denoted by "O" and the plates havingsuch drawbacks were denoted by "X".

(4) Chemical Resistance: The polymer plates were immersed in isopropanoland toluene at room temperature for 24 hours. Afterward, they werescratched with an HB pencil. The plates which were free from any traceswere denoted by "O", and the plates having some traces were denoted by"X".

(5) Workability: The plates which could be abraded by a lens polisherfor spectacle lens processing were denoted by "O", and the plates whichcould not be done were denoted by "X".

                                      TABLE 1                                     __________________________________________________________________________    Test   Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                        Item   55   56   57   58   59   60   61   62   63                             __________________________________________________________________________    Appearance                                                                           ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                  Surface                                                                              5H   9H   9H   4H   4H   9H   6H   9H   9H                             Hardness    or more                                                                            or more        or more   or more                                                                            or more                        Heat   ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                  Resistance                                                                    Chemical                                                                             ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                  Resistance                                                                    Workability                                                                          ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      ◯                                                                      O                              __________________________________________________________________________

EXAMPLE 64

0.1 part of benzoyl peroxide was added to 30 parts of a monomer mixtureprepared by the same procedure as in Example 56, followed by sufficientmixing and defoaming. The mixture was then filtered through a filterhaving a pore diameter of 5 μm under pressure, and then poured into a +2diopter lens mold for diethylene glycol diallyl carbonate. Afterward,polymerization was effected by elevating the temperature of the mixturefrom 70° C. to 140° C. over 3 hours. After cooling, a transparent convexlens having a smooth surface was released from the mold. The pencilhardness on the surface of the convex lens was 9H or more, and arefractive index by the Abbe's refractometer was 1.54.

EXAMPLE 65

0.2 part of benzoyl peroxide was added to 20.0 parts of a monomermixture prepared by the same procedure as in Example 56 followed bymixing and defoaming.

The mixture was then applied onto a steel plate by the use of a coatingbar so that a coating thickness might be 50 μm. Afterward, the mixturewas cured at a temperature of 140° C. for 30 minutes, whereby atransparent coating film having a smooth surface was obtained on thesteel plate. The pencil hardness of this coating film was 9H or more,and the results of a checker test (JIS K 5400) were good. In addition,heat resistance was also good (the specimens were allowed to stand at120° C. for 10 hours in a hot-air drier, and those which were free fromany problems were evaluated to be good).

COMPARATIVE EXAMPLE 1

3.0 parts of benzoyl peroxide was added to 100 parts of diethyleneglycol diallyl carbonate, followed by mixing and defoaming. Thissolution was then poured into a mold prepared by interposing a5-mm-thick polyvinyl chloride spacer between peripheral portions of two5-mm-thick glass plates and then firmly fastening them together with aclamp, and it was tried that polymerization was effected in a hot-airoven for polymerization by elevating the temperature therein from 70° C.to 120° C. over 3 hours. However, when the temperature reached about 70°C. in the course of the polymerization, the polymerization advancedvigorously, so that the polymer was peeled from the glass mold and wascolored yellow.

Only when the polymerization was carried out by elevating thetemperature from 50° C. to 120° C. over 10 hours, a resin plate could beobtained without peeling from the mold, but the pencil hardness of theobtained resin was 3H.

COMPARATIVE EXAMPLE 2

18.8 parts of m-xylylene diisocyanate was added to 20.0 parts of methylmethacrylate, and 0.5 part of dibutyltin laurate was further addedthereto. 26.0 parts of hydroxyethyl methacrylate was slowly addedthereto, while heating was carried out so that an internal temperaturemight be 60° C., thereby obtaining a viscous methyl methacrylate mixtureof an urethane compound in which the infrared spectrum absorption basedon an isocyanate group was scarcely seen. 0.3 part of benzoyl peroxidewas further added thereto, followed mixing and defoaming, and thesolution was then poured into a mold prepared by interposing a5-mm-thick polyvinyl chloride spacer between peripheral portions of two5-mm-thick glass plates and then firmly fastening them together with aclamp, and it was tried that polymerization was effected in a hot-airoven for polymerization by elevating the temperature therein from 45° C.to 120° C. over 3 hours. However, when the temperature reached about 65°C. in the course of the polymerization, the polymerization advancedvigorously, so that the polymer was peeled from the glass mold.

COMPARATIVE EXAMPLE 3

0.5 part of benzoyl peroxide was added to 50 parts of trimethylolpropanetriacrylate, followed mixing and defoaming. This solution was thenpoured into a mold prepared by interposing a 5-mm-thick polyvinylchloride spacer between peripheral portions of two 5-mm-thick glassplates and then firmly fastening them together with a clamp, and it wastried that polymerization was effected in a hot-air oven forpolymerization by elevating the temperature therein from 60° C. to 140°C. over 3 hours. However, at an early stage in the course of thepolymerization, the polymerization advanced vigorously, so that thepolymer was peeled from the glass mold.

Other embodiments of the invention will be apparent to those skilled inthe art from consideration of the specification and practice of theinvention disclosed herein. It is intended that the specification andexamples be considered as exemplary only, with the true scope and spiritof the invention being indicated by the following claims.

What is claimed is:
 1. A high surface hardness transparent resincomprising a crosslinked polymer prepared by copolymerizing a monomer(A) selected from the group consisting of monomers represented by theformulae (V) and (VI) ##STR508## wherein n is 2, R is selected from thegroup consisting of ##STR509## and the substituent on the aromatic ringis present at the m-position or the p-position thereof, ##STR510##wherein n is 3, R is selected from the group consisting of ##STR511##and the substituent on the aromatic ring is present at the m-position orthe p-position thereof and a monomer (B) having, in one molecule, mfunctional groups of at least one kind selected from the groupconsisting of CH₂ ═CH-- C(O)--O--, CH₂ ═C(CH₃)--C(O)--O-- and ##STR512##where the sum of (n+m) is an integer of 3 or more.
 2. A high surfacehardness transparent resin comprising a crosslinked polymer prepared bycopolymerizing a monomer (A) represented by the formula (I) and amonomer (B) wherein formula (I) is: ##STR513## wherein n is an integerof 2 to 4, X is oxygen or sulfur, and R is an aliphatic residue havingor not having an halogen atom, an oxygen atom, an alicyclic ring, aheterocyclic ring or an aromatic ring, an alicyclic residue, or aheterocyclic residue, wherein said monomer (A) is an acid ester selectedfrom the group consisting of carbamic acid ester and thiocarbamic acidester which is obtained by reacting isopropenyl-α, α-dimethylbenzylisocyanate with OH and/or SH group of a compound containing 1-4 OH groupand/or SH groups and an aliphatic residue containing or not containing ahalogen atom, an oxygen atom, an alicyclic ring, a heterocyclic ring oran aromatic ring, an alicyclic residue, or a heterocyclic residue andwherein monomer (B) has in one molecule, m functional groups of at leastone kind selected from the group consisting of CH₂ --CH--C(O)--O--, CH₂═C(CH₃)--C(O)--O-- and ##STR514## and wherein (n+m) is an integer of 3or more.
 3. The high surface hardness transparent resin of claim 2comprising a crosslinked polymer containing at least one structural unitrepresented by the following formula (II) and (III) ##STR515## wherein nis an integer of 2-4, X is oxygen or sulfur, R is an aliphatic residuehaving or not having a halogen atom, an oxygen atom, an alicyclic ring,a heterocyclic ring or an aromatic ring, an alicyclic residue, or aheterocyclic residue, R' is hydrogen or methyl, Y is, similar ordissimilar, ##STR516## and (n+m) is an integer of 3 or more.
 4. The highsurface hardness transparent resin of claim 2 wherein said monomer (A)is an acid ester selected from the group consisting of carbamic acidester and thiocarbamic acid ester which is obtained by reactingisopropenyl-α,α-dimethylbenzyl isocyanate with OH and/or SH group of acompound containing 1-4 OH group and/or SH groups and an aliphaticresidue containing or not containing a halogen atom, an oxygen atom, analicyclic ring, a heterocyclic ring, an aromatic ring, an alicyclicresidue, or a heterocyclic residue.
 5. The high surface hardnesstransparent resin of claim 2 wherein the molecular weight of saidresidue R is from 15 to
 500. 6. The high surface hardness transparentresin of claim 3 wherein the molecular weight of said residue R is from15 to
 500. 7. The high surface hardness transparent resin of claim 2wherein the ratio of said isopropenyl group in said monomer (A) to thetotal of the functional groups selected from the groups selected fromthe group consisting of CH₂ ═CH--C(O)--, CH₂ ═C(CH₃)--C(O)--O-- and##STR517## in said monomer (B) is 1 equivalent: 0.5-10 equivalents. 8.The high surface hardness transparent resin of claim 3 wherein the ratioof said isopropenyl group in said monomer (A) to the total of thefunctional groups selected from the groups selected from the groupconsisting of CH₂ ═CH--C(O)--, CH₂ ═C(CH₃)--C(O)--O-- and ##STR518## insaid monomer (B) is 1 equivalent: 0.5-10 equivalents.
 9. The highsurface hardness transparent resin of claim 1 wherein the ratio of saidisopropenyl group in said monomer (A) to the total of the functionalgroups selected from the groups selected from the group consisting ofCH₂ ═CH--C(O)--, CH₂ ═C(CH₃)--C(O)--O-- and ##STR519## in said monomer(B) is 1 equivalent: 0.5-10 equivalents.